FIELD OF THE INVENTION
[0001] The present invention relates to a semiconductor device having ferroelectric layer
or high dielectric layer as capacitor dielectric layer.
BACKGROUND OF THE INVENTION
[0002] Recently, along with the trend of higher speed and lower power consumption of semiconductor
device such as microcomputer and digital signal processor, electronic appliances for
consumer use are more and more advanced in performance, while an electromagnetic interference
which is an electromagnetic noise generated from these electronic appliances is posing
a serious problem. Accordingly, not only in electronic appliances, but also in semiconductor
devices used in them, measures against electromagnetic interference are demanded.
The most effective measure against electromagnetic interference in the semiconductor
device is to install a capacitor of a large capacitance between the bias line and
ground line inside the semiconductor device, hitherto the capacitor was placed outside
the semiconductor device.
[0003] In addition, lately, nonvolatile random access memories in a simple construction
having a capacitor, using a ferroelectric layer as capacitor dielectric layer, and
dynamic random access memories having a capacitor using dielectric layer of high dielectric
constant as storage capacitor have been developed.
[0004] A conventional semiconductor device having capacitor is specifically described below.
[0005] Fig. 1 is a partially sectional view of a representative semiconductor device. In
Fig. 1, on a silicon substrate 1, an integrated circuit 6 represented by source/drain
active areas 3, a gate oxide 4, and a gate electrode 5 is formed in a region enclosed
by a field oxide area 2. Further on the silicon substrate 1, an insulating layer 7
is formed, and in a specific region on the insulating layer 7, a capacitor 11 consisting
of a bottom electrode 8, a capacitor dielectric layer 9, and a top electrode 10 is
formed. At least covering the capacitor 11, moreover, an interlayer insulating layer
12 is formed. There are also formed interconnections 14a connected to the source/drain
active areas 3 through a first contact hole 13a, interconnection 14b connected to
the bottom electrode 8 of the capacitor 11 through a second contact hole 13b, and
interconnection 14c connected to the top electrode 10 of the capacitor 11 through
a third contact hole 13c. Furthermore, a passivation layer 15 is formed in order to
protect the interconnections 14a, 14b, 14c.
[0006] A manufacturing method of the conventional semiconductor device having capacitor
shown in Fig. 1 is explained below while referring to the flow chart of manufacturing
process shown in Fig. 2, together with Fig. 1. First, at step (1), the integrated
circuit 6 is formed on the silicon substrate 1. At step (2), an insulating layer 7
is formed on a silicon substrate 1. At step (3), a capacitor 11 is formed on the insulating
layer 7. This capacitor 11 is formed by sequentially laminating a first conductive
layer as bottom electrode 8, capacitor dielectric layer 9, and a second conductive
layer as top electrode 10, and patterning respectively by etching. As the capacitor
dielectric layer 9, a ferroelectric layer or high dielectric layer is used, and as
bottom electrode 8 and top electrode 10, a two-layer composition consisting of platinum
layer and titanium layer sequentially from the side contacting with the capacitor
dielectric layer 9 is used. At step (4), an interlayer insulating layer 12 composed
of PSG (phospho-silicate glass) is formed by CVD so that at least the capacitor 11
is covered. At step (5), a first contact hole 13a reaching the source/drain active
areas 3 of the integrated circuit 6, a second contact hole 13b reaching the bottom
electrode 8 of the capacitor 11, and a third contact hole 13c reaching the top electrode
10 of the capacitor 11 are formed. After forming interconnections 14a, 14b, 14c at
step (6), a passivation layer 15 composed of silicon nitride layer or silicon oxynitride
layer of high humidity resistance is formed by plasma CVD at step (7).
[0007] However, in such conventional semiconductor device having capacitor, a PSG layer
is used as interlayer insulating layer 12, and although the purpose of alleviating
the stress to the capacitor 11 is achieved, the moisture generated when forming the
PSG layer by CVD is absorbed by the PSG layer, and this moisture diffuses into the
ferroelectric layer composing the capacitor dielectric layer, thereby lowering the
electric resistance. This phenomenon gives rise to increase of leakage current of
the capacitor 11 or decline of dielectric strength, which may induce dielectric breakdown
of the capacitor dielectric layer 9.
[0008] Yet, in such conventional semiconductor device having capacitor, as a passivation
layer 15, silicon nitride layer or silicon oxynitride layer formed by plasma CVD is
used, and although invasion of moisture from outside into the capacitor 11 may be
prevented, activated hydrogen is generated in the layer forming process by plasma
CVD, and this activated hydrogen may diffuse in the ferroelectric layer or high dielectric
layer for composing the capacitor dielectric layer 9, which may induce increase of
leakage current of the capacitor 11 or deterioration of electrical characteristic.
Generally, the hydrogen atom content in the nitride layer formed by plasma CVD is
as high as 10
22 atoms/cm
3, and by heat treatment after layer forming, diffusion of hydrogen into the capacitor
dielectric layer 9 is accelerated, and the characteristic of the capacitor 11 is further
degenerated.
SUMMARY OF THE INVENTION
[0009] It is hence a primary object of the invention to present a semiconductor device having
capacitor with high reliability.
[0010] In the semiconductor device of the invention, on the interlayer insulating layer
formed on the capacitor, a titanium nitride layer or a titanium-tungsten layer is
formed in a shape for covering the capacitor.
[0011] In this constitution, the titanium nitride layer or titanium-tungsten layer adheres
well to the interlayer insulating layer and is dense, therefore invasion of water
into the capacitor dielectric layer is prevented, and deterioration of the capacitor
does not occur. In addition to this constitution, by forming a silicon nitride layer
in other region than the capacitor, invasion of moisture can be prevented without
applying stress to the capacitor, and the other regions can be completely protected
by the silicon nitride layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Fig. 1 is a partially sectional view showing the structure of principal parts of
a conventional semiconductor device having capacitor.
[0013] Fig. 2 is a flow chart for explaining a conventional manufacturing method of semiconductor
device having capacitor.
[0014] Fig. 3 is a partially sectional view showing the structure of principal parts of
a semiconductor device having capacitor in Example 1.
[0015] Fig. 4 is a flow chart for explaining a manufacturing method of a semiconductor device
having capacitor in Example 1.
[0016] Fig. 5 is a diagram showing the temperature dependence of moisture release amount
from PSG layer.
[0017] Fig. 6 is a diagram showing the electrical reliability of the semiconductor device
having capacitor in Example 1.
[0018] Fig. 7 is a partially sectional view showing the structure of principal parts of
a semiconductor device having capacitor in Example 2.
[0019] Fig. 8, Fig.9, and Fig. 10 are partially sectional views showing a manufacturing
method of semiconductor device having capacitor in Example 2, in which Fig. 8 is a
diagram showing the state of forming interconnections by forming a capacitor on an
insulating layer of a semiconductor substrate in which an integrated circuit is formed,
forming an interlayer insulating layer on the capacitor, and forming contact holes,
Fig. 9 is a diagram showing the state of forming a passivation layer for protecting
the interconnections, and Fig. 10 is a diagram showing the state of forming a second
passivation layer further on the passivation layer in Fig. 9.
[0020] Fig. 11 is a diagram of measuring the leakage current of the capacitor at each step
after forming interconnections of the semiconductor device having capacitor in Example
2.
[0021] Fig. 12 is a diagram showing the relation between the applied voltage to capacitor
and time to breakdown at each step after forming interconnections of the semiconductor
device having capacitor in Example 2.
[0022] Fig. 13 is a partially sectional view showing the structure of principal parts in
a semiconductor device having capacitor in Embodiment 1 of the invention.
[0023] Fig. 14 is a partially sectional view showing the structure of a capacitor in a semiconductor
device in Embodiment 2 of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Before to describe two embodiments of the semiconductor device of the invention,
we will describe two Examples of semiconductors as shown in Figure 3 and Figure 7.
Example 1
[0025] In a semiconductor device of the invention shown in Fig. 3, an isolation oxide layer
32 is formed on a silicon substrate 31, and an integrated circuit 36 represented by
a transistor composed of a diffusion region 33, a gate insulating layer 34, and a
gate electrode 35 is formed in a region enclosed by the isolation oxide layer 32.
[0026] On the silicon substrate 31, an insulating layer 37 composed of silicon oxide layer
is formed, and a capacitor 41 comprising a bottom electrode 38 of platinum layer and
titanium layer, a capacitor dielectric layer 39 composed of ferroelectric layer or
high dielectric layer, and a top electrode 40 composed of platinum layer and titanium
layer is formed on the insulating layer 37. Covering this capacitor 41, an interlayer
insulating layer 42 composed of a PSG layer having the moisture content of 0.5g or
less per 1 cm
3 is formed. In the conventional semiconductor device having capacitor, the moisture
content of the interlayer insulating layer was 0.9g or more per 1 cm
3.
[0027] Above the integrated circuit 36, a first contact hole 43a reaching a diffusion region
33 is formed in the insulating layer 37 and interlayer insulating layer 42, and above
the capacitor 41, a contact hole 43b reaching the bottom electrode 38 and a third
contact hole 43c reaching the top electrode 40 are formed in the interlayer insulating
layer 42. Through the first contact hole 43a, an interconnection 44a composed of aluminum
layer or aluminum alloy layer connected to the diffusion region 33 is formed, and
through the second and third contact holes 43b, 43c, interconnections 44b, 44c composed
of aluminum layer or aluminum alloy layer connected to the bottom electrode 38 and
top electrode 40 are formed. To protect these interconnections 44a, 44b, 44c, a passivation
layer 45 composed of silicon nitride layer or silicon oxynitride layer is formed.
[0028] According to such constitution of Example 1, in the interlayer insulating layer 42,
the moisture content is controlled under 0.5g per 1 cm
3, and if heated in the subsequent steps, diffusion of moisture into the capacitor
dielectric layer 39 can be prevented, thereby preventing increase of leakage current
and a drop in dielectric strength of the capacitor 41, so that a semiconductor device
having the capacitor 41 hardly inducing trouble due to dielectric breakdown as compared
with the prior art may be realized.
[0029] A manufacturing method of such semiconductor device is explained below while referring
to the flow chart of manufacturing method shown in Fig. 4, together with Fig. 3. First,
at step (1), an integrated circuit 36 and others are formed on a silicon substrate
31. At step (2), an insulating layer 37 is formed on the silicon substrate 31. At
step (3), a capacitor 41 is formed on the insulating layer 37. This capacitor 41 is
formed by sequentially laminating a first conductive layer as bottom electrode 38,
a capacitor dielectric layer 39, and a second conductive layer as top electrode 40,
and patterning respectively by etching. As the capacitor dielectric layer 39, a ferroelectric
layer or high dielectric layer is used, and as the bottom electrode 38 and top electrode
40, a two-layer composition consisting of a platinum layer and a titanium layer sequentially
from the side contacting with the capacitor dielectric layer 39 is used. At step (4),
the capacitor 41 is heated to enhance and stabilize the characteristic of the capacitor
dielectric layer 39. At step (5), at least covering the capacitor 41 by CVD or the
like, an interlayer insulating layer 42 composed of PSG layer (photo-silicate glass
layer) is formed, and at step (6), the interlayer insulating layer 42 is heated in
a nitrogen atmosphere, and the moisture contained in the interlayer insulating layer
42 is removed to not more than 0.5g per 1 cm
3 of the interlayer insulating layer 42.
[0030] At step (7), a first contact hole 43a reaching the diffusion region 33 of the integrated
circuit 36, and second and third contact holes 43b and 43c reaching the bottom electrode
38 and top electrode 40 of the capacitor 41 are formed. At step (8), interconnections
44a, 44b, 44c are formed, and at step (9), a passivation layer 45 composed of silicon
nitride layer or silicon oxynitride layer high in humidity resistance is formed by
plasma CVD.
[0031] In the foregoing constitution and manufacturing method, the PSG layer is formed as
interlayer insulating layer 42 by CVD, and the moisture is removed from the PSG layer
in a subsequent heat treatment process, but it is not limited to this, and for example,
a silicon oxide layer may be formed in a condition of high temperature and reduced
pressure, and heat treatment may be omitted.
[0032] In the manufacturing method described above, heat treatment of the interlayer insulating
layer 42 at step (6) in Fig. 4 is conducted in nitrogen gas, but it may be also done
in inert gas such as helium and argon, or in vacuum.
[0033] Results of measurement of moisture adsorption of PSG layer formed by CVD are explained
below by reference to Fig. 5. The abscissa in Fig. 5 denotes the temperature, and
the ordinate represents the amount of moisture released at the corresponding temperature,
and their relation corresponds to the intensity of moisture adsorption. As shown in
Fig. 5, the peak temperature of the adsorbed moisture releasing from the PSG layer
is 300 to 350°C in a first peak, and 450 to 530°C in a second peak. The moisture corresponding
to the second peak is adsorbed to the PSG layer with a sufficiently strong adsorption,
and it seems to hardly affect the reliability in normal use. By contrast, the first
peak drags its foot down to the low temperature side, and water is released in a condition
relatively close to operating temperature, and it seems to induce deterioration of
the capacitor dielectric layer 39.
[0034] It is preferable to heat at 350°C or higher in order to release the adsorbed water
corresponding to the first peak in Fig. 4 right after forming the layer by CVD. Furthermore,
as the interlayer insulating layer 42, heat treatment of silicon oxide layer containing
phosphorus by 6 wt.% or less is found to be preferred also for lessening the stress
applied to the capacitor 41. Besides, the above heat treatment is performed at a not
higher temperature than temperature giving rise to deterioration of a characteristic
of the integrated circuit. The deterioration generally occurs at about 900 °C. It
is preferable to heat at about 850°C or lower.
[0035] The result of evaluation of reliability of the capacitor 41 manufactured in this
Example 1 is shown in Fig. 6. As the capacitor dielectric layer 39, barium strontium
titanate was used. The abscissa denotes the inverse number of electric field applied
to the capacitor 41, and the ordinate represents the time until the leakage current
reaches a specific value. Line (a) shows the leakage current while applying a voltage
to the capacitor 41 manufactured by a conventional method, and the moisture content
of the PSG layer used as interlayer insulating layer 42 was 0.93 g/cm
3. Line (b) relates to the result of the capacitor 41 manufactured in the embodiment,
and the moisture content of the PSG layer as interlayer insulating layer 42 was 0.45
g/cm
3. By comparing these lines, it has been proved that the capacitor 41 of the Example
1 lower in the moisture content of the interlayer insulating layer 42 is superior
by far as compared with the conventional example. Incidentally, the moisture content
in the PSG layer may be 0.5 g/cm
3 or less.
[0036] In the Example 1, after forming and heating the interlayer insulating layer 42, the
contact holes 43a, 43b, 43c are formed, but the sequence of heat treatment may be
changed in the order of formation of interlayer insulating layer 42, formation of
contact holes 43a, 43b, 43c, and heat treatment. In such a case, the contact holes
43a, 43b, 43c serve as vent holes, and moisture adsorbed on the capacitor 41 is released
easily.
[0037] In this Example, the interlayer insulating layer 42 is heated once, but the heat
treatment may be divided in plural steps. For example, a first heat treatment may
be given after forming the interlayer insulating layer 42, and a second heat treatment
after forming the contact holes 43a, 43b, 43c. In this case, the heat treatment condition
may be varied between the first and second heat treatment processes.
Example 2
[0038] A semiconductor device shown in Fig. 7 is a modified example of Example 1 shown in
Fig. 3. What differs between this example and Example 1 is that an interlayer insulating
layer 46 composed of silicon oxide layer is formed on a capacitor 41, and that a passivation
layer 47 composed of silicon nitride layer with hydrogen atom content of 10
21 atoms/cm
3 or less in the layer is formed for protecting interconnections 44a, 44b, 44c of aluminum
layer or aluminum alloy layer.
[0039] According to the constitution of such Example 2, as the interlayer insulating layer
46 contacting directly with the capacitor 41, a silicon oxide layer of low hydrogen
content is used, and as the passivation layer 47, a silicon nitride layer with hydrogen
atom content of 10
21 atoms/cm
3 or less is used, and therefore hydrogen does not permeate the capacitor dielectric
layer 39, and invasion of water from outside into the silicon nitride layer used as
passivation layer 47 can be prevented, so that a semiconductor device excellent in
stability is realized.
[0040] In this example, the passivation layer 47 is a single layer of silicon nitride layer
with hydrogen content of 10
21 atoms/cm
3 or less, but by controlling the thickness of the passivation layer 47 at about 100
nm, if a lamination of silicon oxide layer, silicon nitride layer or silicon oxynitride
layer thereon is used as passivation layer, the same effects are obtained.
[0041] Besides, by forming a silicon oxide layer beneath the passivation layer 47, the stress
applied on the capacitor 41 can be decreased.
[0042] A manufacturing method of this semiconductor device is described below while referring
to Fig. 8, Fig. 9 and Fig. 10. In Fig. 8, an integrated circuit 36 and others are
formed on a silicon substrate 31, an insulating layer 37 is formed thereon, a capacitor
41 is formed on the insulating layer 37, an interlayer insulating layer 46 is formed
to cover the capacitor 41, a first contact hole 43a, and second and third contact
holes 43b and 43c are formed, and interconnections 44a, 44b , 44c are formed, which
may be the same as in a conventional manufacturing method. Next, as shown in Fig.
9, a silicon nitride layer is formed by sputtering to be used as a passivation layer
47.
[0043] In this way, when sputtering is employed as forming method of passivation layer 47,
a dense Si
3N
4 layer of stoichiometric composition can be formed relatively easily at low temperature
of room temperature to 200°C, and damage will not be given to the interconnections
44a, 44b, 44c composed of aluminum layer or aluminum alloy layer. In sputtering, moreover,
since the target and gas does not contain hydrogen atoms, activated hydrogen is not
generated in the layer. The hydrogen atom concentration in the obtained silicon nitride
layer is very low, under 10
21 atoms/cm
3, and if heated after forming the layer, hydrogen hardly diffuses into the capacitor
dielectric layer 39 as far as under 400°C, and the characteristic of the capacitor
41 will not deteriorate.
[0044] Several methods are known for sputtering. For example, in the case of ion beam sputtering
of reactive sputtering with nitrogen ions by using silicon target, it is possible
to form a layer at room temperature. In the silicon nitride layer obtained by ion
beam sputtering, the hydrogen atom concentration is very low, under 10
21 atoms/cm
3, which is equally compared with the silicon nitride layer formed at high temperature
CVD at 800°C. Similar effects are expected in the RF sputtering using silicon nitride,
ceramic target or silicon nitride powder target, or RF planer magnetron sputtering.
[0045] Moreover, as shown in Fig. 10, by forming a second passivation layer 48 made of silicon
nitride layer by plasma CVD on the passivation layer 47 formed in the step shown in
Fig. 9, the thickness of the silicon nitride layer by sputtering may be thin, so that
the stress applied on the capacitor 41 can be decreased.
[0046] As the passivation layer 47, when a silicon nitride layer by sputtering method is
used, by forming a silicon oxide layer beneath the passivation layer 47, the stress
applied on the capacitor 41 can be further decreased.
[0047] By using a barium titanate layer as the capacitor dielectric layer 39, characteristic
changes of the capacitor 41 are described while referring to Fig. 11 and Fig. 12.
In these diagrams, the axis of abscissas shows each step after forming the interconnections
44a, 44b, 44c, in which A is the value after forming the interconnections 44a, 44b,
44c, B is the value after forming the passivation layer 47, and C is the value after
heating for 7 minutes at 380°C in a mixed gas atmosphere of nitrogen and hydrogen
after forming the passivation layer 47. The black circle is a case of forming a silicon
nitride layer as passivation layer 47 by plasma CVD, and the white circle relates
to a case of forming a silicon nitride layer as passivation layer 47 by ion beam sputtering.
Fig. 11 shows the leakage current when a voltage of 1.5 V is applied to the capacitor
41, and Fig. 12 represents the time from application of voltage of 1 MV/cm to the
capacitor dielectric layer 39 at 125°C until breakdown.
[0048] As shown in Fig. 11, as a matter of course, in the case A after forming the interconnections
44a, 44b, 44c, the leakage current is unchanged at 10
-8 A/cm
2 regardless of the forming method of silicon nitride layer, but in the case B after
forming silicon nitride layer on the interconnections 44a, 44b, 44c, the leakage current
increases in the sample forming silicon nitride layer by plasma CVD. This seems because
much activated hydrogen is present in the plasma in plasma CVD, and invades into the
capacitor dielectric layer 39 in the layer forming process, thereby deteriorating
the ferroelectric layer or high dielectric layer composing the capacitor dielectric
layer 39. Further, in the case C after heat treatment, the leakage current is further
increased in the sample forming a silicon nitride layer by plasma CVD. By contrast,
in the samples formed by ion beam sputtering, there is no difference in the leakage
current among samples after steps A, B and C.
[0049] Incidentally, as shown in Fig. 12, in the sample forming a silicon nitride layer
by plasma CVD, the time to dielectric breakdown becomes shorter after every step,
which also seems because hydrogen atoms in the passivation layer 47 invade into the
capacitor dielectric layer 39 to deteriorate the ferroelectric layer or high dielectric
layer for composing the capacitor dielectric layer 39.
[0050] By contrast, in the samples formed by ion beam sputtering, there is no difference
in time to dielectric breakdown among samples after steps A, B, and C.
[0051] In this example, the interconnections 44a, 44b, 44c are constituted of a single layer
of aluminum layer or aluminum alloy layer, and by forming a titanium-tungsten layer
beneath these layers, the adhesion is improved when a platinum layer is used as an
electrode of the capacitor 41, so that the contact resistance can be decreased. the
hydrogen in the capacitor dielectric layer 39 is released in the first heat treatment
process, and oxygen is introduced in the second heat treatment process,thereby recovering
the characteristic of the capacitor dielectric layer 39.
[0052] In this embodiment, the opening 52 corresponding to the capacitor 41 is formed in
the second interlayer insulating layer 51, but the opening 52 may be also provided
in correspondence to the top electrode 40, instead of the entire capacitor 41, and
the hydrogen in the capacitor dielectric layer 39 can be similarly released in the
heat treatment process.
Embodiment 1 of the invention
[0053] A semiconductor device of the invention shown in Fig. 13 is a modified example of
Example 2 shown in Fig.7. What differs between this embodiment and Example 2 is that
first conductive layers 53a, 53b, 53c made of titanium layer and second conductive
layers 54a, 54b, 54c made of titanium nitride layer are formed beneath interconnections
44a, 44b , 44c, including first contact hole 43a, second contact hole 43b, and third
contact hole 43c, and that the top of the capacitor 41 is covered with the first conductive
layer 53c, second conductive layer 44c, and interconnection 44c through an interlayer
insulating layer 46, forming a passivation layer 55 composed of silicon nitride layer
or silicon oxynitride layer, covering the interconnections 44a, 44b, 44c.
[0054] In such constitution of Embodiment 1, when a layer not passing hydrogen is selected
as the second conductive layer 54c, if a silicon nitride layer or a silicon oxynitride
layer is formed as passivation layer 55 by plasma CVD, reduction of the capacitor
dielectric layer 39 by hydrogen atoms, radicals, or ions in the plasma can be prevented.
[0055] As the first conductive layers 53a, 53b, 53c, titanium layers or titanium-tungsten
layers are preferable, and as the second conductive layers 54a, 54b, 54c, titanium
nitride layers are preferable. Or, by using a combination of first conductive layer
53c and interconnection 44c in the layer covering over the capacitor 41, and omitting
the second conductive layer 54c, deterioration of the capacitor dielectric layer 39
may be prevented in the process of forming the passivation layer 55 as compared with
the prior art.
Embodiment 2 of the invention
[0056] Fig. 14 is a modified example of Embodiment 1, and integrated circuit and others
not related directly with the embodiment are omitted in the drawing. What differs
between this embodiment and Embodiment 1, is that the top of the capacitor 41 is covered
with a first conductive layer 56a and an interconnection 44c through an interlayer
insulating layer 46, and that the first conductive layer 56a and interconnection 44c
are partly overlapped in the peripheral part of the capacitor 41, and also that a
second interlayer insulating layer 57 composed of silicon nitride layer possessing
an opening 58 corresponding to the top electrode 40 of the capacitor 41 is provided.
[0057] In such constitution, invasion of water from the top of the capacitor 41 is blocked
by the first conductive layer 56a composed of titanium-tungsten layer or the like,
while the other regions are shut off by the second interlayer insulating layer 57
composed of silicon nitride layer or the like, so that the reliability about humidity
resistance and water resistance may be more effectively enhanced.